INTRODUCTION

Established in 1962, Tata International is an international marketing company with a global

turnover of US$ 850 million in 2006-07. It is a trading company with business lines that include
leather, engineering and pharmaceutical products. It has a worldwide reach provided by a well-
integrated network, that encompasses its subsidiaries, offices, joint ventures and alliances, with
business hubs in South Asia, South East Asia, Europe and Africa catering to its markets in
Europe, SAARC, ASEAN, the Far East, and Africa.

Tata International is India's leading leather and leather products exporter. As a leather and
leather products exporter, the company operates its leather business in India from Dewas,
Chennai, Delhi, Calcutta, as well as, from China, South Asia and the Middle East, leveraging our
global network. We source wet blue worldwide and have world-renowned clients for our finished
leather and leather products.

Our state-of-the-art manufacturing facility at Dewas in Central India is among the top three
worldwide for goat skin. Our units have ISO 9001 certification from RW TUV CERT of
Germany since 1994, making ours the first leather-manufacturing facility in India to receive this
certification. The leather unit in Dewas is the first in the industry in Asia to be ISO 14000
certified. Our facilities are governed by International Labour Organization laws.

Our R&D department has made internationally acknowledged break-through in the production of
chrome free leather and processing of solid waste. We have established and co-ordinate a highly
flexible supply chain for sourcing leather, footwear, garments and leather goods.

As a leather and leather products exporter our main markets are the quality stringent markets of
Western Europe, North America and the Far East.

As leading leather garments exporter from India flexibility is our strength. With 25 years of
experience in this fashion industry, we as leather garments exporter are aware that one must
respond quickly to a change in needs. We cater for this through our capacity to produce 1000
garments per day, with the aid of our well-trained in-house designers, world class manufacturing
processes and special sample lines to meet customer's requirements.

We became a leather garments exporter in 1975. The Dewas based (in Madhya Pradesh, India)
Leather Garments division of Tata International, adopted best in class manufacturing processes
and systems in collaboration with one of the premier leather manufacturers of Germany -
Lederman.

Today Tata International has one of the most modern and well-equipped manufacturing facilities
on the South Asian subcontinent. Apart from being the first leather garments unit in India to
boast ISO 9001 and ISO 14001 certification (certificates awarded by RW TUV of Germany), we
as a leather garments exporter also enjoy the patronage of an established international clientele
that includes names like Betty Barclay, Escudo, Karlstad, Kaufof, C&A, Marks & Spencer’s,
Talenti, Gerry Weber, Mango (Spain), Stallman and Mauritius.
Tata companies operate in seven business sectors: communications and information technology,
engineering, materials, services, energy, consumer products and chemicals. They are, by and
large, based in India and have significant international operations. The total revenue of Tata
companies, taken together, was $70.8 billion (around Rs325,334 crore) in 2008-09, with 64.7 per
cent of this coming from business outside India, and they employ around 357,000 people
worldwide. The Tata name has been respected in India for 140 years for its adherence to strong
values and business ethics.

Every Tata company or enterprise operates independently. Each of these companies has its own
board of directors and shareholders, to whom it is answerable. There are 27 publicly listed Tata
enterprises and they have a combined market capitalisation of some $60 billion, and a
shareholder base of 3.5 million. The major Tata companies are Tata Steel, Tata Motors, Tata
Consultancy Services (TCS), Tata Power, Tata Chemicals, Tata Tea, Indian Hotels and Tata
Communications.

Tata Steel became the sixth largest steel maker in the world after it acquired Corus. Tata Motors
is among the top five commercial vehicle manufacturers in the world and has recently acquired
Jaguar and Land Rover. TCS is a leading global software company, with delivery centres in the
US, UK, Hungary, Brazil, Uruguay and China, besides India. Tata Tea is the second largest
branded tea company in the world, through its UK-based subsidiary Tetley. Tata Chemicals is
the world’s second largest manufacturer of soda ash and Tata Communications is one of the
world’s largest wholesale voice carriers.

In tandem with the increasing international footprint of Tata companies, the Tata brand is also
gaining international recognition. Brand Finance, a UK-based consultancy firm, recently valued
the Tata brand at $9.92 billion and ranked it 51st among the world's Top 100
brands. Businessweek magazine ranked Tata 13th among the '25 Most Innovative Companies' list
and the Reputation Institute, USA, recently rated it 11th on its list of world's most reputable
companies.

Founded by Jamsetji Tata in 1868, Tata’s early years were inspired by the spirit of nationalism. It
pioneered several industries of national importance in India: steel, power, hospitality and
airlines. In more recent times, its pioneering spirit has been showcased by companies such as
TCS, India’s first software company, and Tata Motors, which made India’s first indigenously
developed car, the Indica, in 1998 and recently unveiled the world’s lowest-cost car, the Tata
Nano.

Tata companies have always believed in returning wealth to the society they serve. Two-thirds of
the equity of Tata Sons, the Tata promoter company, is held by philanthropic trusts that have
created national institutions for science and technology, medical research, social studies and the
performing arts. The trusts also provide aid and assistance to non-government organisations
working in the areas of education, healthcare and livelihoods. Tata companies also extend social
welfare activities to communities around their industrial units. The combined development-
related expenditure of the trusts and the companies amounts to around 4 per cent of the net
profits of all the Tata companies taken together.
Going forward, Tata is focusing on new technologies and innovation to drive its business in India
and internationally. The Nano car is one example, as is the Eka supercomputer (developed by
another Tata company), which in 2008 was ranked the world’s fourth fastest. Anchored in India
and wedded to traditional values and strong ethics, Tata companies are building multinational
businesses that will achieve growth through excellence and innovation, while balancing the
interests of shareholders, employees and civil society.

Finished Leather:

Tata International's Finished Leather range includes Full Aniline and Semi Aniline finishes in
Kid, Goat, Sheep, Cow and Buffalo. We also offers Patent leathers from Cow, Goat and Sheep,
plus Suede and Nubuck from Kid and Cow. Our experience of over 25 years in Finished Leather
has made us the largest supplier of Kid and Goat skin Finished Leather from India. We are
capable of exporting finished leather items as per your need, in any quantity and are capable to
meet your import requirements round the year.

Products offered and capacity:

Leather Articles: Tata International produces high quality leather products and is one of the
largest exporters of the same. The product range comprises of a wide array of leather goods
ranging from personal articles to business and travel accessories.

The medium-end is serviced by our dedicated units in Calcutta and Dewas. The Calcutta
operations cater to the German, UK and US market in the middle value segment. Here we have
dedicated units capable of producing in excess of 50,000 pcs of small leather goods per month.

Tata International products are created taking into consideration style, aesthetics, craftsmanship
and functionality. Our talented crafts-persons hand craft the creations from some of the finest
Indian and Imported leathers with the most stringent in-process checks and refinements to ensure
the right quality.

Tata International brings to leather goods manufacturing 25 years of experience in leather

tanning and sourcing, its highly skilled workforce and an understanding of customer quality
requirements developed over the years by working with our highly discerning customers. We are
proud to be associated with world renowned brands.

Footwear: Tata International is India's leading footwear manufacturer and exporter. Versatile
and flexible manufacturing facilities in Dewas, Chennai and New Delhi in India, reinforced with
state of the art production units have helped Tata International emerge as a leading footwear
manufacturer and exporter.

As a footwear manufacturer and exporter we have a high-end full shoe facility, Graziella Shoes
Limited located at Chennai, established in a 50-50 Joint Venture with Pucci SRL of Italy. This
footwear manufacturing facility produces 3,000 pairs per day of Full Shoes with Italian Unit
Soles and Indian Uppers. The high-quality shoes are sold to well establish brands.
As a footwear manufacturer and exporter we also have a Hong-Kong operation where we
outsource the manufacture of shoes to China and then export these to third countries. The leather
for these shoes is either supplied from India or purchased from Pakistan or Indonesia. The China
sourcing is only for bulk business of 10,000 - 15,000 pairs per style.

Qualified and experienced designers, trained at reputed international design schools, proficient in
CAD software and digital photography, man the in-house design centres at the facilities of this
footwear manufacturing facility in Dewas and Chennai (in India). The design process includes
last identification, pattern development, testing, prototype development and grading. The
designers cater to the customer's design requirements, which include new developments of lasts,
styles and features based on current forecasts and fashion trends. Designers and product
development engineers from our customers also visit and work with our designers It is this
committed care as a footwear manufacturer that has earned us a clientele that includes well-
established European shoe brands and catalogue houses.

Capacity:

The plant and machinery is being continuously upgraded to keep pace with the rapid
development in trade and our product development and R&D,which is manned by highly
qualified professionals enable the leather finishing unit come out with niche product and keep
itself abreast with new developments.

1,50,000 sq. ft of finished leather per day.

400 colours are processed in a month and our speciality is that we can match any pantone shade.
There is high flexibility in production lot size and computerised colour matching.

Tata International actively participates in MODEUROP and in every season colours developed
here have been selected.

Capacity: The leather garments units of Tata International located at Dewas in Central India and
Chennai in southern India have a capacity for 25,000 pieces per month of high quality leather
garments.

Workforce: The leather garments unit employs an extremely skilled workforce of 700 people at
various locations in the country. There are well-trained in-house designers and an in house
quality control, which looks after the quality systems and production systems at every single
stage of production.

Technical Hardware: The garments units are equipped with over 300 state-of-the-art stitching
machines (Pfaff, Durkopp and Adler) and other special purpose machines.
Fair and Exhibitions: Tata International Limited is a regular participant in the leading
leather fairs in the world.

 Leather Show Hongkong

 PLW, Pirmasesns, Germany
 Lineapelle, Bologna, Italy
 GDS Fair, Dussoldorf, Germany
 British Footwear Fair, Birmingham, UK
 The Shoe Show, Las Vegas, USA

At these fairs, we display the company's range of finished leathers based on MODEUROP
shades and our range of leather footwear, garments and articles.

Our interaction with our customers at these fairs helps us forecast fashion trends and offer
Spring-Summer and Autumn-Winter colours to our customers.

Forms of leather:

 Vegetable-tanned leather is tanned using tannin and other ingredients found in

vegetable matter, tree bark, and other such sources. It is supple and brown in color, with
the exact shade depending on the mix of chemicals and the color of the skin. It is the only
form of leather suitable for use in leather carving or stamping. Vegetable-tanned leather
is not stable in water; it tends to discolor, and if left to soak and then dry it will shrink
and become less supple and harder. In hot water, it will shrink drastically and partly
gelatinize, becoming rigid and eventually brittle. Boiled leather is an example of this
where the leather has been hardened by being immersed in hot water, or in boiled wax or
similar substances. Historically, it was occasionally used as armor after hardening, and it
has also been used for book binding.
 Chrome-tanned leather, invented in 1858, is tanned using chromium sulfate and other
salts of chromium. It is more supple and pliable than vegetable-tanned leather, and does
not discolor or lose shape as drastically in water as vegetable-tanned. It is also known as
wet-blue for its color derived from the chromium. More esoteric colors are possible using
chrome tanning.
 Aldehyde-tanned leather is tanned using glutaraldehyde or oxazolidine compounds.
This is the leather that most tanners refer to as wet-white leather due to its pale cream or
white color. It is the main type of "chrome-free" leather, often seen in shoes for infants,
and automobiles. Formaldehyde tanning (being phased out due to its danger to workers
and the sensitivity of many people to formaldehyde) is another method of aldehyde
tanning. Brain-tanned leathers fall into this category and are exceptionally water
absorbent. Brain tanned leathers are made by a labor-intensive process which uses
emulsified oils, often those of animal brains. They are known for their exceptional
softness and their ability to be washed. Chamois leather also falls into the category of
aldehyde tanning and like brain tanning produces a highly water absorbent leather.
 Chamois leather is made by using oils (traditionally cod oil) that oxidize easily to
produce the aldehydes that tan the leather to make the fabric the color it is.
 Synthetic-tanned leather is tanned using aromatic polymers such as the Novolac or
Neradol types. This leather is white in color and was invented when vegetable tannins
were in short supply during the Second World War. Melamine and other amino-
functional resins fall into this category as well and they provide the filling that modern
leathers often require. Urea-formaldehyde resins were also used in this tanning method
until dissatisfaction about the formation of free formaldehyde was realized.
 Alum-tanned leather is tanned using aluminium salts mixed with a variety of binders
and protein sources, such as flour and egg yolk. Purists argue that alum-tanned leather is
technically "tawed" and not tanned, as the resulting material will rot in water. Very light
shades of leather are possible using this process, but the resulting material is not as supple
as vegetable-tanned leather.
 Rawhide is made by scraping the skin thin, soaking it in lime, and then stretching it
while it dries. Like alum-tanning, rawhide is not technically "leather", but is usually
lumped in with the other forms. Rawhide is stiffer and more brittle than other forms of
leather, and is primarily found in uses such as drum heads where it does not need to flex
significantly; it is also cut up into cords for use in lacing or stitching, or for making many
varieties of dog chews.

Leather types:

 Full-grain leather refers to the upper section of a hide that previously contained
the epidermis and hair, but were removed from the hide/skin. Full-grain refers to hides
that have not been sanded, buffed, or snuffed (as opposed to top-grain or corrected
leather) in order to remove imperfections (or natural marks) on the surface of the hide.
The grain remains in its natural state allowing the best fiber strength and durability. The
natural grain also has natural breathability, resulting in less moisture from prolonged
contact. Rather than wearing out, it will develop a natural patina over time, with some
cracking and splitting. The finest leather furniture and footwear are made from full-grain
leather. For these reasons, only the best raw hide is used to create full-grain leather. One
way to test if leather is full-grain is to lightly scratch its surface with your nail. If it leaves
a lighter-colored streak, it's full-grain. Full-grain leathers are typically available in two
finish types: aniline and semi-aniline.

• Top-grain leather is a misnomer: it gives the false impression that it is "top" quality. In
fact, full-grain is the highest quality. Top-grain leather is the second-highest quality. Its
surface has been sanded and refinished. As a result, it has a colder, plastic feel, less
breathability, and will not develop a natural patina. However, it does have 2 advantages
over full-grain leather: it is typically less expensive, and has greater resistance to stains.

• Corrected-grain leather is any leather that has had an artificial grain applied to its
surface. The hides used to create corrected leather are of inferior quality that do not meet
the high standards for use in creating vegetable-tanned or aniline leather. The
 imperfections are corrected and an artificial grain applied. Most corrected-grain leather is
used to make pigmented leather as the solid pigment helps hide the corrections or
imperfections. Corrected grain leathers can mainly be bought as two finish types: semi-
aniline and pigmented.

• Split leather is leather created from the fibrous part of the hide left once the top-grain of
the rawhide has been separated from the hide. During the splitting operation, the grain
and drop split are separated. The drop split can be further split (thickness allowing) into a
middle split and a flesh split. In very thick hides, the middle split can be separated into
multiple layers until the thickness prevents further splitting. Split leather then has an
artificial layer applied to the surface of the split and is embossed with a leather
grain (Bycast leather). Splits are also used to create suede. The strongest suedes are
usually made from grain splits (that have the grain completely removed) or from the flesh
split that has been shaved to the correct thickness. Suede is "fuzzy" on both sides.
Manufacturers use a variety of techniques to make suede from full-grain. For example, in
one operation, leather finish is applied to one side of the suede, which is then pressed
through rollers; these flatten and even out one side of the material, giving it the smooth
appearance of full-grain. Latigo is one of the trade names for this product. Reversed
suede is a grained leather that has been designed into the leather article with the grain
facing away from the visible surface. It is not a true form of suede.

The International Union of Leather Technologists and Chemist Societies have a glossary of
leather terms that can be found at IULTCS.

Other less-common leathers include:

• Buckskin or brained leather is a tanning process that uses animal brains or other fatty
materials to alter the leather. The resulting supple, suede-like hide is usually smoked
heavily to prevent it from rotting.

• Patent leather is leather that has been given a high-gloss finish. The original process was
developed in Newark, New Jersey, by inventor Seth Boyden in 1818. Patent leather
usually has a plastic coating.

• Shagreen is also known as stingray skin/leather. Applications used in furniture

production date as far back as the art deco period. The word "shagreen" originates
from France and is commonly confused with a shark skin and stingray skin combination.

• Vachetta leather is used in the trimmings of luggage and handbags, popularized

by Louis Vuitton. The leather is left untreated and is therefore susceptible to water and
stains. Sunlight will cause the natural leather to darken in shade, called a patina.

• Slink is leather made from the skin of unborn calves. It is particularly soft, and is valued
for use in making gloves.
 • Deerskin is one of the toughest leathers, partially due to adaptations to their thorny and
thicket filled habitats. Deerskin has been prized in many societies including indigenous
Americans. Most modern deer skin is no longer procured from the wild, with deer farms
breeding the animals specifically for the purpose of their skins. Large quantities are still
tanned from wild deer hides in historic tanning towns such
as Gloversville and Johnstown in upstate New York. Deerskin is used in jackets and
overcoats, professional sporting equipment for martial arts such as kendo and bogu, as
well as high-quality personal accessories like handbags and wallets. It commands a high
price due to its relative rarity and proven durability.

• Nubuck is top-grain cattle hide leather that has been sanded or buffed on the grain side,
or outside, to give a slight nap of short protein fibers, producing a velvet-like surface.

There are two other descriptions of leather commonly used in specialty products, such as
briefcases, wallets, and luggage.

• Belting leather is a full-grain leather that was originally used in driving pulley belts and
other machinery. It is often found on the surface of briefcases, portfolios, and wallets, and
can be identified by its thick, firm feel and smooth finish. Belting leather is the only kind
of leather used in luxury products that can retain its shape without the need for a separate
frame; it is generally a heavy-weight of full-grain, vegetable-tanned leather.

• Nappa leather, or Napa leather, is chrome-tanned and is extremely soft and supple and is
commonly found in higher quality wallets, toiletry kits, and other personal leather goods.

The following are not 'true' leathers, but contain leather material. Depending on jurisdiction, they
may still be labeled as "Genuine Leather."

• Bonded leather , or "reconstituted Leather", is not really a true leather but a man-made
material. Some types of bonded leather are composed of 90% to 100% leather fibers
(often scrap from leather tanneries or leather workshops) bonded together with latex
binders to create a look and feel similar to that of 'true' leather at a fraction of the cost.
This bonded leather is not as durable as other leathers, and is recommended for use only
if the product will be used infrequently. An example for the use of this type of bonded
leather is in Bible covers. The term "bonded leather" when used to describe upholstered
furniture is a different product and construction. Bonded leather upholstery is a vinyl
upholstery that contains about 17% leather fiber in its backing material. Hence, there is
no leather in the surface of this product. The vinyl is stamped to give it a leather-like
texture.Bonded leather upholstery is durable and its manufacturing process is more
environmentally-friendly than leather production.

• Bycast leather is a split leather with a layer of polyurethane applied to the surface and
then embossed. Bycast was originally made for the shoe industry and recently was
adopted by the furniture industry. The original formula created by Bayer was strong, but
expensive. Most of the Bycast used today is very strong and durable product. The result
 is a slightly stiffer product that is cheaper than top grain leather but has a much more
consistent texture and is easier to clean and maintain.

Leather production processes:

The leather manufacturing process is divided into three fundamental sub-processes: preparatory
stages, tanning and crusting. All true leathers will undergo these sub-processes. A further sub-
process, surface coating can be added into the leather process sequence but not all leathers
receive surface treatment. Since many types of leather exist, it is difficult to create a list of
operations that all leathers must undergo.

Tanning is the process which converts the protein of the raw hide or skin into a stable material
which will not putrefy and is suitable for a wide variety of end applications. The principal
difference between raw hides and tanned hides is that raw hides dry out to form a hard inflexible
material that when re-wetted (or wetted back) putrefy, while tanned material dries out to a
flexible form that does not become putrid when wetted back. There is a large number of different
tanning methods and materials that can be used, the choice is ultimately dependent on the end
application of the leather. The most commonly used tanning material is chromium, which leaves
the leather once tanned a pale blue color (due to the chromium), this product is commonly called
“wet blue”. The hides once they have finished pickling will typically be between pH of 2.8-3.2.
At this point the hides would be loaded in a drum and immersed in a float containing the tanning
liquor. The hides are allowed to soak (while the drum slowly rotates about its axle) and the
tanning liquor slowly penetrates through the full substance of the hide. Regular checks will be
made to see the penetration by cutting the cross-section of a hide and observing the degree of
penetration. Once a good even degree of penetration exists, the pH of the float is slowly raised in
a process called basification. This basification process fixes the tanning material to the leather
and the more tanning material fixed the higher the hydrothermal stability and increased
shrinkage temperature resistance of the leather. The pH of the leather when chrome tanned
would typically finish somewhere between 3.8-4.2.

Crusting is when the hide/skin is thinned, retanned and lubricated. Often, a coloring operation is
included in the crusting sub-process. The chemicals added during crusting have to be fixed in
place. The culmination of the crusting sub-process is the drying and softening operations.
Crusting may include the following operations:wetting back, sammying, splitting, shaving,
rechroming, neutralization, retanning, dyeing, fatliquoring, filling, stuffing, stripping, whitening,
fixating, setting, drying, conditioning, milling, staking, and buffing.
For some leathers a surface coating is applied. Tanners refer to this as finishing. Finishing
operations may include: oiling, brushing, padding, impregnation, buffing, spraying, roller
coating, curtain coating, polishing, plating, embossing, ironing, ironing/combing (for hair-
on), glazing and tumbling.

Role of enzymes in leather production: Enzymes like proteases, lipases and amylases have an
important role in the soaking, dehairing, degreasing, and bating operations of leather
manufacturing.

Proteases are the most commonly used enzymes in leather production. The enzyme used should
not damage or dissolve collagen or keratin, but should be able to
hydrolyze casein, elastin, albumin and globulin-like proteins, as well as non-structured proteins
which are not essential for leather making. This process is called bating.[1]

Lipases are used in the degreasing operation to hydrolyze fat particles embedded in the skin.

Amylases are used to soften skin, to bring out the grain, and to impart strength and flexibility to
the skin. These enzymes are rarely used.

Preservation and conditioning of leather: The natural fibers of leather will break down with
the passage of time. Acidic leathers are particularly vulnerable to red rot, which causes
powdering of the surface and a change in consistency. Damage from red rot is aggravated by
high temperatures and relative humidities, and is irreversible.

Exposure to long periods of low relative humidities (below 40%) can cause leather to become
desiccated, irreversibly changing the fibrous structure of the leather.

Various treatments are available such as conditioners, but these are not recommended
by conservators since they impregnate the structure of the leather artifact with active chemicals,
are sticky, and attract stains.

Description:

The present invention relates to a process for finishing leather by spray application of optionally
water-containing organic solutions in an electrostatic field.

The hitherto most widely practiced process for finishing leather is spraying in an airstream or
spraying airless, since these methods make it possible to obtain the best effects in respect of
handle, outward appearance and rub and flex fastness properties.

On the other hand, this process also has a number of serious disadvantages. There are primarily
the high spray losses of the material to be applied. Moreover, it requires the use of very dilute
solutions (i.e. having solids contents of only about 2-4%), which makes it virtually impossible to
recover the solvent from the waste air in an economically reasonable manner.
It has therefore already been proposed (cf. DE-A-3,611,729) to spray pieces of leather with
finishing solutions in an electrostatic field.

This basically elegant process, however, has failed to become established in practice since,
although it cuts down on spray losses, it does not reduce the absolute amount of organic solvents.

If, then, it is attempted to use concentrated solutions in an electrostatic field, it is generally

observed that compared with the conventional spraying in an airstream or airless there is a
deterioration in spray performance and spray distribution; that is, except for the more efficient
application of the material being sprayed the process described in DE-A-3,611,729 does not offer
any significant advantages.

It has now been found, surprisingly, that the disadvantages of the existing processes for finishing
leather can be largely overcome if the finishing liquors are sprayed from the start into a water
and/or solvent atmosphere which has a residual oxygen content of at most 15% by volume.

This novel process solves two important existing problems: it permits the use of highly
concentrated spraying liquors and it permits the treating of the solvent-containing waste air in an
economically acceptable manner.

The solids content of the finishing liquors can be up to 50% and the viscosity at the operating
temperature can be up to 10,000 cP. Preference is given to using liquors which at the operating
temperature have a viscosity of 500-5,000 cP. In general, the operating temperature is 20°-40° C.
(i.e. approximately room temperature). However, in the case of very viscous polymercontaining
liquors the temperature can also be raised to 60°-80° C. to reduce the viscosity.

The residual oxygen content of the solvent atmosphere is preferably less than 10, particularly
preferred less than 7, % by volume.

The atmospheric oxygen content is reduced to these values by the introduction of inert gases,
such as, for example, nitrogen, argon, CO2 or in certain circumstances even water vapour.

The solvent content of the solvent atmosphere should be 10-100%, preferably 15-90%,
particularly preferably 25-75%, of the saturation concentration. This is because if the solvent
concentration is too close to saturation point, there may occur isolated instances of condensation
and undesirable droplet formation. The solvents used for producing this atmosphere are
preferably the same substances as are used for preparing the spray solution.

Suitable solvents are all the solvents used in the finishing of leather, such as, for example, esters,
ketones, ethers, ether alcohols, alcohols, ether esters and aromatic hydrocarbons. Furthermore,
the finishing liquors may contain customary leather auxiliaries, such as, for example,
crosslinkers, waxes, dyestuffs, fillers, delustrants, pigments, handle control agents, viscosity
regulators, dryness-standardizing agents and the like.
Basically, it is possible to use in the novel process all the polymers used in leather finishing, such
as cellulose esters (nitrocellulose, cellulose acetobutyrate), polyamides, polyurethanes, polymers
and copolymers of vinyl chloride, vinylidene chloride and vinyl acetate, etc.

It is also possible to process highly reactive 2-component systems of the type described for
example in DE-A-3,309,992 by this technique. It is preferable to use here an electrostatic spray
gun with an upstream mixing system as described for example in DE-A-2,746,188.

By the novel process it is possible to produce finishes for high-grade leathers of the type required
in the furniture and automotive upholstery sector, it being particularly worth emphasizing that
the pieces of leather, on appropriate drying, are immediately stackable following finishing.

The invention will be further described with reference to the accompanying drawing wherein:

FIG. 1 is a schematic of the apparatus used to carry out the process.

To carry out the novel process use is advantageously made of the spray booth depicted in FIG. 1,
which is equipped essentially with two measuring positions, an oxygen meter, an inert gas and
compressed air supply, a spray nozzle for the solvent, venting means, a spray bell, a finishing
liquor, a high-voltage generator, transportation means for the workpiece and an earthed support
table.

Before use the booth is rendered insert, for example with nitrogen, and sealed gas-tight. The
oxygen of the air is displaced by the introduction of for example nitrogen (4) to less than 15,
preferably less than 10, % by volume. Thereafter the interior of the spray booth is saturated with
solvent. This solvent is sprayed into the spray booth through a spray gun (6) installed in the
booth wall until 10-100% (preferably 15-90%) of the saturation concentration has been reached.

To measure the oxygen, the oxygen-containing gas is removed at measuring positions (1) and (2)
and the oxygen content is determined by means of an oxygen meter (3). It is not until the safety
value of 15% by volume or less of O2 has been reached that the finishing process can be started
by switching on the high voltage (10).

The finishing is carried out for example by the principle of the electrostatic high-speed rotation
spraying process. By means of this electrostatic spraying technique a high-voltage field is
generated between the spray bell (9) and the earthed workpiece (leather) (11). The liquid to be
spray dispensed is pumped out of the finishing liquor (8) into the bell (9) rotating at a high speed
and is finely atomized there. The atomized finish particles become negatively charged at the bell
rim and are then guided by means of the electrostatic field forces to the earthed workpiece,
where they deposit and release their charge. The earthed support table (13) transmits its earthing
to the workpiece. It is of course also possible to apply the solutions using normal spray nozzles,
i.e. an atomizing process which is carried out airless or with air.

After the finishing process has ended, the leather is transported out of the spraying zone by
means of the transportation means (12). The solvent-charged atmosphere can be disposed of
through the venting exit (7), for example by freezing out or absorbing the solvent, which can
optionally be recirculated. If necessary, the interior of the spray booth can be ventilated with
compressed air (5).

The detailed process conditions are described in the following examples:

EXAMPLE1

a) A solution of product I (see below) was processed at 20° C. on an electrostatic spraying range
of the Ransburg design. The electrostatic spraying range was installed in a booth which was
filled with a gas mixture which by continuous inflow and outflow was changed a total of 15
times per hour and which consisted of a mixture of room air/oxygen in which the oxygen content
was below 5% by volume.

The setting of the spray bell was adjusted to

a)control air 1.2 bar ring air 3.5 bar revolutions 10-35,000 rpm of the bell voltage 70 KV
The solution was spray dispensed, but the only result was intensive thread formation in the air
gap between bell and substrate of the type described colloquially as "spinning". Changes in
respect of control air, ring air or speed of rotation had no effect.

b) Example 1a was repeated, except that the spray booth was charged with a gas mixture of
nitrogen/diacetone alcohol (DAA), the booth atmosphere being saturated with DAA (10-11 g of
DAA/m3 of booth space). The result was a spray cone where no "spinning" was observable. On
impingement of the product on the substrate--in this case a piece of cardboard to determine the
amount of add-on--the solution spread out and formed a smooth film.

EXAMPLE 2

a) An experiment working with a 1:1 solution of product I in toluene/isopropanol 30% strength

was carried out in the machine setting and in an atmosphere as in Example 1b at 25° C. The
turbine of the bell barely revolved, since the viscosity of the solution was too high (viscosity at
20° C. was 200 cP).
b) Example 2a was repeated, except that the solution was heated to 80° C. and the speed of the
turbine was set to 35,000 rpm. The result is a spray in which the solution was very well dispersed
in droplet form, there was no sign of "spinning", and the spray cone had the ideal bell shape, and
which leveled out on the leather to form a very good and uniform finish (the viscosity of the
solution was 600 cP at the application temperature).

EXAMPLE 3

100 g of the solution of Example 2b were admixed with 20 g of a 20% strength solution of
cellulose acetobutyrate in 60:40 acetone/diacetone alcohol. This solution was likewise readily
spray-dispensable.

EXAMPLE 4

a) A 30% strength aqueous dispersion of product II was spray dispensed in the booth, which was
filled with room air, in accordance with the following recipe:
3 parts of the PU dispersion 30% strength (18% solids content) 2 parts of water 0.4 part of a
carbon black colouring.

The liquor had a viscosity which is characterized by an efflux time of 13" in the 4 mm Ford cup.
Although the dispersion had a viscosity suitable for spray dispensing, the result was a poor spray
distribution. The droplets of spray impinging on the substrate were already so dry at the surface
that adequate flow was impossible.

b) Batch and machine setting as in Example 4a, except that the atmosphere in the spray booth
was changed by blowing in diethyl ketone/water vapour and nitrogen. The material was
satisfactorily sprayable, and the levelling on the substrate was immaculate.

EXAMPLE 5

A PUR reactive system which at RT has a viscosity of about 3,000 cP and a solids content of
90% was spray dispensed.

Composition
50 parts of the PES/polyurethane/NCO prepolymer mentioned under product III 50 parts of the
PE/polyurethane/NCO prepolymer mentioned under product III 15 parts of a mill base in
cyclohexane of an iron oxide pigment of brown colour 5 parts of a silicone oil 10 parts of
methoxypropyl acetate and 5 parts of diethylene glycol.
The batch was not sprayable in this consistency (of 12,000 cP at 20° C.), but on warming to 80°
C. the viscosity was reduced to 600 cP and the batch because sprayable with very good levelling
properties.

The control air was adjusted to 3 bar; the turbine had a speed of 40,000 rpm.

EXAMPLE 6

As a modification of Example 1 of DE-A-2,637,115 the following experiment was carried out:

Two metering pumps, one for prepolymer A (see below) and the other for hardener 1, were used
to convey into a mixing chamber incorporating a mixer as described in EP-A-1,581, where
mixing took place with the aid of nitrogen and the mixture was sprayed with a spray gun
provided with a spray electrode onto an oppositely charged (earthed) mould adhesively bonded
to an aluminium plate. Owing to the solvent present in the spray booth atmosphere, the levelling
of the sprayed material on the mould was excellent. The composition sprayed onto the mould
leveled out in the manner of a film and began to set after about 1 minute, calculated from the
time of spraying. The reacting composition had placed on top of it the split leather to be coated,
which was pressed in place. The total coating then passed through a hot drying duct at 80° C.
After about 6 minutes, calculated from the time of spraying, the coating was peeled without
tackiness from the mould.

The polyurethane urea layer had a thickness of 0.22-0.25 mm.

The coated split leather had a grain confusingly similar to natural leather, and after a short time it
was dry, stackable and processible on conventional shoe machines. The adhesion between
coating and split leather was excellent, and the handle was pleasantly dry.

EXAMPLE 7

A prepolymer was prepared from equal parts by weight of a polydiethylene glycol adipate
(molecular weight 2,000) and polyethylene glycol (molecular weight 400) by means of
isophorone diisocyanate, and the prepolymer was advanced with hydrazine hydrate to a
polyurethane urea. Polyurethane was present as a 40% strength solution in 3:3:1
toluene/isopropanol/2-methoxypropanol. The solution had a viscosity which was not
measureable in a DIN cup (4 mm; DIN 53211); (in a Haake viscometer the viscosity was more
than 20,000 cP at 22° C.). Nor was it sprayable.

The dilution with the same solvent mixture as in Example 8 to a viscosity of 85 seconds (180 cP
at 22° C.) and a concentration of 14.5% produced a solution which was still not sprayable by the
airless technique but which was already excellently processible according to the invention.
By the airless technique this product was conventionally processible only at a concentration of
11.4% and a viscosity of 17 seconds.

EXAMPLE 8

1 part of a polyurethane of hexane diisocyanate (3.5 parts) and (96.4 parts) of polyester of
butanediolhexanediol polyadipate (molecular weight 5,000) and trimethylolpropane (0.04 part)

and 2 parts of a cellulose acetobutyrate were dissolved at 15% strength in a 1:1 mixture of ethyl
acetate and butyl acetate. The solution had a viscosity of 70 seconds in a DIN cup (200 cP at 22°
C.). By the method of the invention it was excellently sprayable, but by the airless technique it
only became sprayable on dilution to below 8% (viscosity: 20 seconds).

In what follows, the products used above are described in more detail.

Product I

One-component thermoplastic polyester-polyurethane as 30% strength solution in 1:1

toluene/isopropanol consisting of an adipic acid/hexanediol polyester having an average
molecular weight of 2,000 reacted with isophorone diisocyanate in a molar ratio NCO:OH of 1:1.

Product II

30% strength diethyl ketone/water (1:9) dispersion of a polyester urethane consisting of a

polyester of adipic acid/dihydroxypropionic acid/hexanediol having a molecular weight of 1,600
with free COOH groups, which serve as hydrophilic free COOH components, saturation of the
free COOH components by an aliphatic diamine and reaction of the resulting polyester with
isophorone diisocyanate at a molar ratio NCO/OH of 1:1.

Product III

A highly reactive 2-component polyurethane as described in DE-A-2,637,115, consisting of a

70% strength polyester prepolymer of adipic acid/hexanediol of molecular weight 2,000 reacted
with TDI-2,4 in a molar ratio NCO:OH of 2:1 and dissolved in toluene with an 80% solids
content. It is used together with a polyetherpolyurethane consisting of 4,4'-
diisocyanatodiphenylmethane and a polyether consisting of polypropylene glycol ether
(molecular weight 2,000) (NCO:OH=2:1) in the mixing ratio of 1:1.

Prepolymer A
A reactor is charged with 444 g of 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane
(isophorone diisocyanate). At room temperature, 9 g of 1,4-butanediol, 9 g of trimethylolpropane
and 1,600 g of a hydroxy polyester of adipic acid, ethylene glycol, diethylene glycol and 1,4-
butanediol having a hydroxyl number of 56 and a molecular weight of 2,000 were added in
succession with stirring. The reaction mixture was heated and maintained at 110° C. for about 1
hour (until NCO is constant). After cooling down to 65° C., the reaction mixture was diluted
with 412 g of methyl ethyl ketone and 206 g of toluene, corresponding to a 77% strength
solution.

The prepolymer solution had a viscosity at 20° C. of 1,000 cP.

Hardener 1

A mixture of 170 g of 3,3,5-trimethyl-5-aminomethyl-cyclohexylamine (IPDA), 13 g of water

and 417 g of methyl ethyl ketone was refluxed for 2 hours. After cooling down, the mixture was
ready for use as a hardener.

Of the 170 g (1 mole) of IPDA used, there were present in the mixture:

A) 12.9 mol% as free IPDA

B) 41.6 mol% as ##STR1## c) 45.5 mol% as the bis-methyl ethyl ketone ketimine of IPDA

The mixture also contained in total 37.88 g of water.

LEATHER TANNING PROCESS:

Leather tanning is a process in which chemical agents and extracts are applied to various types of
hides and skins in order to prevent rotting. Not all tanneries follow the same method of
processing hides into leather. However, the process described here is used by the majority. First,
the hides must be prepared for tanning at the packing house. This includes unhairing (a lime
solution loosens the hair, making removal easier), fleshing (cleaning off the inner side of the
hides), and bating (removing the lime from the hides). Next, the skins and hides are cured salted
or soaked in brine to preserve them until they reach the tannery. Once at the tannery, the hides
are soaked to remove the salt. Two primary methods are used to then convert the raw material
into leather: chrome tanning and vegetable tanning. The method used depends on the intended
use of the leather. Chrome tanning, which involves the use of soluble chromium salts such as
chromium sulfate, is used primarily to tan leather for the upper parts of shoes. Vegetable tanning,
which uses tannic acid, is used to tan heavy leather for shoe soles, bags, straps, harnesses, and
other products used in industrial equipment. Chrome tanning is the most widely used method in
the United States.
Several basic stages are involved in the tanning process. First, the underlying layer of the hide is
"split" off and shaved to uniform thickness. Tanning drums are then used to saturate the hides in
the tanning solution, which preserves the hide and adds strength. The hides are tanned again,
where dyes and oils are added to provide, color, softness, and durability. Then the hide must be
stretched and dried to remove all excess moisture. At this point, the leather is firm, flat, and
ready to be trimmed. Finally, the hide is conditioned and finished. The finishing process involves
softening the hide mechanically, spraying final colors onto the leather to meet customer
requirements, and embossing to the required texture.